Process of producing water-insoluble azo dyestuffs on the fiber and dyeing preparations therefor



Gil

Patented Oct. 10, 1939 PRDCESS F PRODUCING WATER-TNSOLU- BLE AZO DYESTUFFS ON THE FIBER AND DYEING PREPARATIONS THEREFOR Karl Jellinek, Ofienbach-on-the-Main, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application April 21, 1938, Serial No. 203,445. In Germany April 23, 1937 11 Claims.

The present invention relates to a process of producing water insoluble azo dyestuiis on the fiber and to dyeing preparations therefor.

In the production of azo dyestufis'on the fiber there are added to the developing bath s buffer- .lng substances capable of preventing damage of the diazo solution by the alkali of the grounding solution. As alkali binding agents of this kind aluminium sulfate, zinc sulfate and magnesium sulfate are preferred. The salt is advantageously mixed with the commercial dye-salt so that the dyer has at his disposal a diazo preparation which, by simple dissolution in water, yields a developing bath ready for dyeing and requiring no further addition, as is necessary'if, for instance, acetic acid is used as alkali binding agent.

The use of these buffering substances, however, involves certain disadvantages insofar as they are liable to form with the textile oils present in the grounding solution-generally Turkey red oilrnetel soaps which are, for the most part, oi a sweaty consistency and can deposit on the fiber; this may spoil the spinning capacity of loose material and may lead to wetting defects oi'piece, goods, whereby the 'dyeings obtained are non-uniform;

I have found that. such disadvantages are avoided by conducting the coupling operation in the presence oi a water-soluble chromic salt. As

such salts there may be used, for instance, chromic suliate, chromic fluoride or chromic acetate. The ohm-mic salts are very suitable as alkali binding agents. When used with diazo compounds of feeble coupling power they do not give rise to insumcient yields of dyestufi, as is oftenthe case when aluminium sulfateor zinc sulfate is used, and have the advantage over magnesium sulfate that they have a feebly acid reaction and thus influence favorably the clarity of the dyeings. Furthermore, there are not formed iniurious deposits on the fiber so that a better and more uniiorm appearance of the goods is guaranteed.

which of the chromic saitsin question is most suitable for attaining an optimum dyeing with the selected base can be ascertained in an easy manner by a preliminary tests.

It is also possible previously to mix watersoluble chromic salts with diazonium-compounds, which have separated in solid form, from bases suitable for the preparation of ice-colors, or with bases of this kind in admixture with the quantity of nitrite as is necessary for the diazotization, or with such bases or their mineral acid salts. In the first case dyeing preparations are obtained which yield by simple dissolution in water dye-baths ready for use, whereas the dyeing preparations furthermore mentioned allow to prepare developing baths by introduction into mineral acids or by simple diazotization. The dyeing preparations thus obtained are distinguished by their stability, even when they con- 1. 29.75 grams of zinc chloride double salt of diazotized Z-amino-6-benzoylamino-4- .methor -1-methylbenzene in the form of a press cake of 80 per cent. strength are triturated to a homogeneous powder together with I so grams of anhydrous, sodium sulfate and 50 grams of chromlc acetate.

A dyeing preparation is obtained which by simple dissolution in water yields developing solutions ready for use.

Instead of chromie acetate the same quantity of chromic fluoride may be used.

i 2. 49.88 grams of the zinc chloride double salt of diazot'ized 1-amino-4-benzoylamino-2.5- diethoxybenzene in the form of a moist press cake aredehydrated under reduced pressure and finely triturated infadmixture with d ll grams of chromic formate and ill grams of sodium sulfate.

A dyeing'preparatio'n is obtained which by simpie dissolution in water yields developing solutions ready for use.

3. 30 grams of the diazonium chloride from 4- amino-4'-methoxydiphenylamine dried under reduced pressure are flnely triturated together with 65 grams of chromic acetate.

A dyeing preparation is obtained which by simple dissolution in water yields developing solutions ready for use.

4. 26 grams of the diazonium chloride from 4- amino-diph'enylamine dried under reduced pressure are finely triturated with 85 grams of chromic oxalate and 10 grams of anhydrous sodium sulfate.

A dyeing preparation is obtained which by simple dissolution in water yields a developing solution ready for use.

5. 40 grams of the zinc chloride double salt of tetrazotized dianisidine are dried under reduced pressure, mixed with grams of anhydrous sodium sulfate and 40 grams of chromic fluoride and triturated.

A dyeing preparation is obtained which by simple dissolution in water yields a developing solution ready for use.

8. 18.2 grams of the hydrochloride of 1-amino-\ 3-chlorobenzene of 90 per cent. strength are triturated together with 23.8 grams of hydrous chromic sulfate. A stable preparation is obtained which when diazotized in the usual manner and neutralized yields dye baths ready for use.

'7. grams of the hydrochloride of 85 per cent. strength of 4-chloro-2-aminodiphenyl ether are mixed with 12 grams of hydrous chromic fluoride. A stable preparation is obtained which when diazotized in the usual manner and neutralized yields dye baths ready for use.

8. 28.5 grams of the hydrochloride of l-amino- 2-methoxy benzene-5-sul1onic acid-diethylamide of 90 per cent. strength are triturated together with 33 grams of hydrous chrome alum. A stable preparation is obtained which when diazotized in the usual manner and neutralized yields dyebaths ready for use.

In the same manner the corresponding quantity or metaaminoazotoluene or 2.4-dibromo-1- aminbnaphthalene may be mixed with the quantity of hydrous chrome alum indicated above. Also in this .case a stable preparation is obtained which when diazotized in the usual manner and neutralized yields dye-baths ready for use.

9. 18.3 grams of 5-nitro-2-amino-1-methoxybenzene are mixed with 8 grams of sodium nitrite and 12 grams-.of hydrous chromic fluoride. A stable preparation is obtained which may be diazotized by introduction into dilute hydrochloric acid and which yields after neutralization by means of sodium acetate developing solutions ready for use in dyeing.

10. 31.1 grams of the zinc chloride double salt of diazotized l-amino'anthraquinone are mixed in the form of amoist press cake together with 10 grams of anhydrous sodium sulfate and 60 grams of hydrous chromic acetate. After drying a stable dyeing preparation is obtained which by dissolution in water yields dye-baths ready for use.

11. Cotton yarn is impregnated in'the vat 30 C. in a solution containing per liter 2.3-hydroxynaphthoylaminobenzene--grams- 6 Caustic soda solution of34 B cc 9 Formaldehyde of 33 per cent. strength cc.. 6 Turkey red oil m 10 for 30. minutes, the proportion of the goods to the liquor being 1:20; the yarn is squeezed and developed in the vat for 20 minutes, the proportion of the goods to the liquor being 1:20, in a diazo-solution which has been neutralized with sodium acetate and contains the amount of diazocompound corresponding with 3.5 grams of 1-amino-2-nitro-4-chlorobenzene per liter, and to which 0.8 gram of chromic chloride per liter has been added. After thoroughly rinsing, while cold, and, if necessary, acidifying, the dyeing is after-treated at boiling temperature for 30 minutes with a solution containing 3 grams of soap and 1 gram of calcined sodium carbonate per liter. A yellowish red tint is thus obtained.

12. Cotton yarn is impregnated in a solution prepared as described in Example 11 and containing per liter 7 grams of 1-(2'.3'-hydroxynaph- -thoylamino) -2-methylbenzene, the dyeing is then developed in a diazo-solution prepared in the usual manner, neutralized with sodium acetate and containing the amount of diazo-compound corresponding with 1.3 grams of 1-amino-3- chlorobenzene per literand 0.55 gram of chromic fluoride, and is after-treated in the usual manner.

A reddish orange tint is obtained.

Instead of the diazo-solution prepared from the base there may be used the solution of a dye preparation which contains 0.55 gram of chromic fluoride for the quantity of diazonium compound corresponding with 1.8 grams of 1-amino-3- chlorobenzene in the form of the acid 1.5-naphthalene-disulfonate, and one of the usual adjuvants.

13. Cotton yarn is impregnated in the usual manner in a solution containing per liter- 1-(2'3'-hydroxynaphthoy1amino) 2; methoxybenzene grams 5 Caustic soda solution of 34 B cc 7.5 Formaldehyde of 33 per cent, strength--cc 5 Turkey red oil cc 10 squeezed and developed in a diazo-solution, neutralized by means of sodium acetate which contains the quantity of diazo-compound corresponding with 1.4 grams of 1-amino-2-methyl- 5-chlorobenzene and 1.4 grams of hydrous chromic sulfate per liter, and after-treated in the usual manner.

A clear scarlet tint is obtained.

Instead of the diazo-solution prepared from the base there may be used the solution of a diazo-salt preparation containing for the quantity of diazo-compound corresponding with 1.4

grams of 1-amino-2-methyl-5-ch1orobenzene in the form of the acid 1.5-naphthalene-disulfonate, 1.4 grams of hydrous chromic sulfate and one of the usual adjuvants.

14. 80 grams of 1-amino- 2-methyl-4-chlorobenzene hydrochloride of 90 per cent. strength are triturated with 22 grams of chromic fluoride to form a homogeneous powder.

2.55 grams of this mixture are diazotized in the usual manner, neutralized by means of sodium acetate and made up to one liter. A diazo-solution is obtained which contains per liter 0.5 5 gram of chromic fluoride and the quantity of diazo-compound corresponding with 1.4 grams of 1-amino-2-methyl-4-chlorobenzene.

Cotton-yam is developed in this bath in the usual manner. The yarn has previously been grounded with a solution prepared as described in Example 11 from 4 grams of 1-(2'.3'-hydroxynaphthoylamino) 2-methyl-4-chlorobenzene per liter.

Alter the usual after-treatment there is obtained a clear bluish red tint.

15. Cotton yarn is impregnated at C. in the vat with-a solution containing per liter- 1 (223' hydroxynaphthoylamino) 2.4 dimethoxy-S-chlorobenzene gra.ms v 3 Caustic soda solution of 34 B cc 6 Formaldehyde of 33 per cent. strength -cc 3 Turkey red oil or 10 squeezed and developed in the vat in a dim-- solution, neutralized by means of sodium acetate and containing per liter the amount of diazocompound corresponding with 2.85 grams of 1- amino -2 methoxybenzene-5 sulionyl-diethylamine and 3.2 grams of chromic acetate, the yarn is then after-treated in the usual manner.

A clear bluish red tint is thus obtained.

16. Cotton piece goods are impregnated on a Ioulard with a solution prepared in the usual manner from 1 -(2'.3' hydroxynaphthoylamino) mapmnalane grams 10 Caustic soda solution of 34 B -cc 20 Turkey red oil cc 15 then dried and developed on a foulard in a diazosolution neutralized by means of sodium bicarbonate and containing per liter the amount of diam-compound corresponding with 5.5 grams of 4.4-diamino-3.3-dimethoxy-diphenyl and 14 .grams of chromic acetate. The dyeing is thoroughly rinsed, while cold, and soaped at boiling temperature for a short time. I

An even reddish blue tint is obtained.

17. A mixed tissue, consisting of viscose artiflcial silk and cotton, is padded with a solution containing per liter- 2.3--hydroxynaphthoyl-aminobenzene grams 12 Caustic soda solution of 34 as cc 1% Turkey red oil cc 20 and then dried.

The material thus treated is then developed on. a ioulard in a solution prepared by diazotizing 12.5 grams of l-amino-i-benzoylamino-Zfi-di and are dried.

The material thus treated is then developed on 'a Ioulard with a solution prepared by diazotizing l1 grams-oi l-amino-4-benzoylamino-25 diethoxybenzene, neutralizing by'means of sodi- 'urn bicarbonate, adding lfi grams of chromic acetate and making up to 1 liter. material is rinsed and soaped at boiling temperature.

An indigo blue piece dyeing is obtained.

finally the I By using insteadof 2.3-hydroxynaphthoylaminobenzene the l-(2'.3'-hydroxynaphthoylainino)-2-methyl-4-chlorobenzene, there is also obtained an even indigo blue piece dyeing having a good through-dyeing efiect.

A blue-green. dyeing is obtained by using 1- (2'- hydroxyanthracene-3- carbonylamino) Z-methylbenzene as coupling component.

19.'44.9 grams of press cake of 78 per cent. strength of 4-methoxy-diphenylamine-4-diazonium chloride are triturated to a homogeneous powder with 9.4 grams of anhydrous sodium sulfate and 45.7 grams of chromic acetate. 100 grams of a diazo-salt are obtained which is very stable to storage and contains per cent. of 4'-methoxy-diphenylamine-4 1 diazonium chloride.

. Bleached cotton material is padded on a ioulard in a solution containing per liter-- 2.3-hydroxynaphthoyl-aminobenzene grams" 15 Caustic soda solution of 34 B cc 22.5 Turkeyred oi1 cc 20 and then dried.

The material thus treated is developed by pass ing it on a foulard through a solution containing per liter 43.7 grams of the above described dyesalt from 4-aniino-4'-methoxy-diphenylamine, squeezed, rinsed after a passage in the air for 30 seconds, and soaped at boiling temperature.

A very uniform blue tint is obtained.

The same good result is attained if instead of the cotton material there is used a material made from artificial silk staple fibers.

20. Bleached cotton fabric is padded on a foulard in a solution containing per liter- 2.3-liydroXynaphthoyl-aminobenzene grams 15 Caustic soda solution of 34 Be cc 22.5 Turkey red oil cc 20 and then. dried. I

The fabric thus treated is printed (a) with a printing paste containing per kilo- Gra ns Lactic acid of 50 per cent. strength 200 Water 300 Neutral starch-tragacanth-thiclrening 500 and (b) with a printing paste containing per kilo- Acid. 1.s-nap neutralized by means of sodium ,carbonate, of cliazotized l-amino-Z-methyl =4; chlorobenzene grams" 32 Crystallized aluminum sulfate do 80 After drying the fabric is passed through a solution of the following composition:

Diazonium chloride of 4-amin0-diphenylamim gram Crystallized chromic acetate do artificial silk staple fiber is padded in a solution containing per liter-- 2.3-hydroxynaphthbylaminobenzenegrams 12 Turkey red oil cc. 15 Caustic soda solution of 34 B cc. 18 and then dried. v

The fabric thus treated is printed withthe following printing paste:

Grams Diazonium chloride of 4-amino-4'-methoxydiphenylamine Crystallized chromic acetate 24 Neutral starch-tragacanth-thickening 500 Water 467 After drying, the fabric is passed through a hot sodium carbonate solution (2 grams of calcined sodium carbonate per liter), then rinsed and soaped.

A deep fast blue print or very good evenness is obtained.

22. Cotton piece goods are impregnated on a foulard in a solution containing per liter 10 grams of 1-(2'-hydroxycarbazole-3-carbonylamino) -4- chlorobenzene, 20 cc. of caustic soda solution of 34 B. and 15 cc. of Turkey red oil and dried. The dyeing is then developed on a foulard in a diazo solution, neutralized with sodium bicarbon- .ate and containing the amount of diazo-compound corresponding with 5 grams of 1-amino-2- methoxy-E-chlorobenzene per liter and 14 grams of chromic acetate per liter. A uniform tobacco brown dyeing is obtained. v

23. Cotton piece goods are impregnated on a foulard in a solution containing per liter 10 grams of 1- 3 -hydroxydiphenylene-oxide-2 -carbonylamino)-2.5-dimethoxybenzene, 20 cc. of caustic soda. solution of 34 B. and 15 cc. of Turkey red oil and dried. The dyeing is then developed on a foulard in a diazo solution, neutralized with sodium bicarbonate and containing the amount of diazo-compound corresponding with 7 grams of 1.- amino-Z-methoxybenzene-5-sulfonic acid-diethylamide per liter and 14 grams of chromic acetate per liter. A uniform dark brown dyeing is obtained.

24. Cotton yarn is impregnated in the vat at 30 C. in a solution containing per liter 1.5 grams of 1- (2'-hydroxy-7.8-benzocarbazole-3'-carbonylamirio) -4-methoxybenzene, 3 cc. of alcohol, 6.5 cc. of caustic soda solution of 34 B., 10 cc. of Turkey red oil and 1.5 cc. of formaldehyde of 33 per cent. strength, for 30 to 40 minutes, the proportion of the goods to the liquor being 1:20; the yarn is squeezed and developed in the vat for 20 minutes, the proportion of the goods to the liquor being 1:20, in a diazo solution which has been neutralized with prepared chalk and mixed with 1 gram of chromic acetate and contains the amount of 'diazo compound corresponding with 1.65 grams of 1-amino-2-methoxy-4-nitrobenzene per liter. After thoroughly rinsing the dyeing is soaked at boiling temperature for 30 minutes. A deep greenish black tint is thus obtained.

I claim:

1. Process of producing water-insoluble azo dyestuffs on the fiber according to the ice-color method which comprises developing the vegetable fiber impregnated with a coupling component adapted for the production of ice-colors in a solution of a diazonium salt containing a water- 3. Process of producing water-insoluble azo dyestuffs on the fiber according to the ice-color method which comprises developing the vegetable 1 fiber impregnated with a 2.3-hydroxynaphthoic acid arylamide in a solution of a diazonium salt containing chromic acetate as alkali binding agent. I

4. Process of producing a water-insoluble azo dyestuif on the fiber according to the ice-color method which comprises developing the vegetable fiber impregnated with 1-(2.3'-hydroxynaphthoylamino) -2-methyl-4-chlorobenzene in a solution of diazotized 1-amino-4-benzoylamino-2.5- diethoxybenzene containing chromic acetate as alkali binding agent.

5. Process of producing water-insoluble azo dyestuffs on the fiber according to the ice-color method which comprises developing the vegetable fiber impregnated with a coupling component adapted for the production of ice-colors in a solution of a diazo-preparation comprising a diazonium salt in solid form and a water-soluble chromic salt.

6. Process of producing water-insoluble azo dyestuffs on the fiber according to the ice-color method which comprises developing the vegetable fiber impregnated with a 2.3-hydroxynaphthoic arylamide in a solution' of a diazo-preparation comprising a diazonium salt in solid form and a water-soluble chromic salt.

7. Process of producing water-insoluble azo dyestuffs on the fiber according to the ice-color method which comprises developing thevegetable fiber impregnated with a 2.3-hydroxynaphthoic acid arylamide in a solution of a diazo-preparation comprising a diazonium salt in solid form and chromic acetate.

8. Process of producing a water-insoluble azo dyestuif on the fiber according to the ice-color method which comprises developing the vegetable fiber impregnated with 2.3hydroxynaphthoylaminobenzene in asolution of a diazo-preparation comprising 4-methoxydiphenylamine-i-ediazonium chloride, chromic acetate and anhydrous sodium sulfate.

9. Preparations for dyeing and printing comprising a diazonium salt in solid form and a water-soluble chromic salt.

10. A preparation for dyeing and printing comprising the diazonium chloride from 4-amino-4 

